Rosin ester-modified alkyd resin



July 19, 1949. l c. D. ENDER l 2,476,714

nosIn asma-MODIFIED 111.11m RESIN med'neo. 5, 194e 0.8 0.9 MOLS OF PHTHALIC ACIVD PER MOL 'OF' TOTAL DICARBOXYLIC ACID CLARENCE o. ENDER INVENTof AGENT Patented July 19, 1949 UNITED STATES PATENT OFFICE ROSIN ESTER-MODIFIED ALKYD RESIN clarence n. Ender, wnmngton, nel., mmma Hercules Powder Company, Wilmington, Dei., a corporation of Delaware Application December 5, 1946, Serial No. 714,186

9 Claims. (Cl. 260-26) This invention relates to synthetic resins and to methods for the preparation thereof. More particularly, it relates to reaction products of dihydric alcohols, alpha-beta-unsaturated dicarboxylic acids, phthalic acid, and monohydric alcohol esters of a rosin acid and to methods for their preparation.

'In U. S. patent application S. N. 490,645, iiled June 12, 1943 now Patent No. 2,411,904, there are described resins prepared from a dihydric alcohol, an alpha-beta-unsaturated dicarboxylic acid and a monohydric .alcohol ester of a rosin acid, these resins being characterized by fusibility, by sol-l ubility in benzene and ethyl acetate and by a phenol red acid number less than 50. These resins have the unique characteristics of substantial stability to heat at temperatures below 150 C. and at the same time the capacity to be cured to an infusible state by heat at above 200 C. This characteristic is obviously an important one and one which suggests many applications in the commercial arts, such as hot-melt coating, etc.

An important disadvantage, however, attends the use of these resins in conjunction with vinyl resins. particularly the vinyl acetate-chloride copolymer. Compatible i'llms containing the resin and copolymer can be obtained by dispersing the ingredients in the usual solvents for the copolymer and laying the lms down immediately.

The dispersions, however, even when freshly pre` pared are cloudy. They become more cloudy with age and the ingredients nally settle out. Unless the dispersions are used immediately after preparation, the resulting lms are of a heterogeneous nature and clearly evidence incompatibility of the ingredients. These resins may, accordingly,

' be said to lack solution compatibility with vinyl cannot be used immediately after preparation.

In accordance with this invention, it has now been found possible to overcome this disadvantage by employing in the preparation of the resin a portion of phthalic acid in replacement for part of the alpha-beta unsaturated dicarboxylic acid. The amount of phthalic acid employed is critical and may be varied from about 0.10 to about 0.67 mol per mol of total dicarboxylic acid, depending upon the amount of monohydric alcohol ester of rosin acid employed as shown in Figure l. Resins prepared on the basis of these critical amounts of phthalic acid have the capacity to form permanently clear solutions with vinyl acetate-chloride copolymer resins in the usual solvents ior such copolymer resins. They are also characterized by having substantially lower viscosities in thel molten state as compared with resins of S. N. 490,645. At the same time, the resins retain the unique thermosetting properties of the resins described in application S. N. 490,645, ipe., they have substantial stability to heat at temperatures below 150 C. but have the capacity to be cured to an'infusible state at temperatures above 200 C. and have a cure time (defined infra) at 200 C. of less than 4 minutes.

The resinous reaction products of this invention are accordingly prepared from a dihydric alcohol, an alpha-beta-unsaturated dicarboxylic acid, phthalicl acid and a monohydric alcohol ester of a rosin acid. The dihydric alcohol is employed inthe amount of from 0.70 to 1.50 mois per mol of total dicarboxylic acid. The nonalcoholic reactants are employed in amounts as defined by the area ABC of Figure l.

The examples following illustrate typical procedures in accordance with the invention:

Example 1 A resin was prepared on the basis of the following raw material formulation:

. Parts (A) Phthalic anhydride 10.9 (B) Maleic anhydride 21.5 (C) Ethylene glycol- 22.0 (D) Methyl ester of rosin 92.2

Reactants A, B and C were charged into areaction kettle and heated at 20D-210 C. for a period of about 2 hours until the acid number of the mixture was 65. Reactant D was then added and the temperature raised to 26o-265 C. The reaction was continued at this temperature for a period of about 6 hours, during the last 4 hours This resin was characterized by the capacity to formv permanently clear solutions with vinyl acetate-chloride copolymers, for example, vinyl acetate-chloride copolymer (Vinylite VYLF) and the resin of this example in all proportions formed permanently clear solutions in cyclohexanone (l5-25% solids). Films laid down from this solution showed the ingredients to be entirely compatible. The resin of this example could be heated at temperatures below C. for extendedA periods of time without any substantial build up in viscosity. Upon heating the resin in film form at temperatures above 200 C., howover, the resin cured to an infusible state.

' resulting resin had the i'ollowing properties:

Examine 2 A resin was prepared on the basis of the following raw material formulation:

Parts (A) Phthalic anhydride 74 (B) Maleic anhydride 196 (C) Ethylene glycol 188 (D) Methyl ester o! rosin 789 Reactants A, B, and C were reacted for a period oi about 2 hours at a temperature within the range of 193-206 C. to produce a product having an acid number of 60. At this point, '189 parts o! reactant D were added and the reaction continued at a temperature of 251-263 C. for a period oi' about 4 hours, during the last hour oi which the reaction mass was sparged with carbon dioxide. This product had the following properties:

Acid number 4.9 Curing time seconds.- 44

This resin formed-permanently clear solutions with vinyl acetate-chloride copolymers. was stable to heat at temperatures below 150 C. and had curing characteristics similar to the Example 1 resin at temperatures above 200 C. v

Example 3 A resin was prepared on the basis ot the iollowing raw material formulation:

Parts (A) Phthalic anhydride 3.3 (B) Maleic anhydride 19.6 (C) Ethylene glycol 16.5

(D) Methyl ester of rosin 105.2

Reactants A, B and C were charged into a reaction kettle and heated at 195-210" C. for about 1.5 hours until the acid number was 40. Reactant D wasthen added and the temperature raised to 2GB-270 C. The reaction was continued at this temperature for 5.5 hours, using a nitrogen gas sparge during the last 4 hours. The

Acid number 2.8 Drop melting point C 62.5 Curing time seconds 115 This resin had the compatibility and heat stability characteristics of the resin of Example l. Films of the resin could be cured by heating at temperatures above 200 C. The resin possessed excellent gasoline resistance.

Example 4 A resin was prepared on the basis of the following raw material formulation:

(A) Phthalic anhydride 19.7

(B)v Maleic anhydride 11.5

(C) Ethylene glycol 19.4

(D) Methyl ester of rosin 49.5

Ingredients A, B, and C were heated at 195-210 C. for 1.8 hours to obtain a product having an acid number of 59. Ingredient D was added and the mixture heated at 260-270 C. for 3.5 hours.

l The reaction mixture was spargedwith nitrogen duringthe last 2 hours. The. resulting resin had the following properties:

Acid number 2.2 Drop melting point C 73 Curing time seconds-- 40 l This resin formed permanently clearsolutions with vinyl acetate-chloride copolymers and was stable to heat at temperatures below 150 C. It had curing characteristics similar to the resin ol' Example 1 at temperatures above 200 C.

Example 5 A resin was prepared on the basis ot the following raw material formulation:

Parts (A) Phthalic anhydride 5.9 (B) Maleic anhydride 10.6 (C) Ethylene glycol 10.6 (D) Methyl ester of rosin 50.1

All ingredients were heated up to a maximum temperature or 260-270 C. Vover a period of 3 hours at which point a resin having an acid number of 16 was obtained. Heating was continued at 260270 C. until a cure time of the resin was seconds. The final resins had these properties:

Acid number '1.8 Drop melting point C 77 Curing time seconds 125 The compatibility and heat stability characteristlcs of this resin were substantially the same as those of the resin ci' Example 1.

Example 6 A resin was prepared on the basis of the following raw material formulation:

. Parts (A) Phthalic anhydride 3.0 (B) Fumaric acid 20.0 (C) Diethylene glycol 25.3 (D) Methyl ester of rosin 62.3

Reactants A, B and C were heated at 195-210 C. for 1.2 hours at which point the product had an acid number or 45. Reactant D was added and heating continued at 260-270" C. for 1.5 hours. The ilnal product had the following properties:

Acid number 1.1 Drop melting point C 54 lCuring time seconds 24 This resin was compatible withvinyl acetatechloride copolymers (Vinylite VYHH) in the ratios of l: 3, 1:1 and 3:1. Permanently clear solutions were obtained from the ingredients in these proportions in the usual solvents for vinyl acetate-chloride copolymer resins, as for example cyclohexanone. The resin per se was stable to heat at temperatures below C., but could be cured by heating iilms thereof at temperatures above 200 C.

Example 7 A clear lacquer was prepared on the basis of the following formulation. A 25% solids solution of Vinylite VYHH in a solvent; composed of equal parts of toluene and acetone was prepared. Vinylite VYHH is a vinyl acetate-chloride copolymer comprising 85-88% vinyl chloride and having and free from tack. Paper coated with thel lacquer exhibited no blocking tendency.

The examples illustrate the use o! maleic cording to this invention. However, any alphabeta-unsaturated dicarboxylic acid or -the anhydride of such acid may be substituted; Thus.

maleic r`acid, maleic anhydride, fumarie acid,`

itaconic acid and the like are suitable. The anhydrides of the alpha,betaunsaturated dicarboxylic acids and the acids themselves are equivalently operable in this invention.

The dihydric alcohol utilized in the method of this inventionv may be in general any dihydric alcohol which, aside fromthe hydroxy groups, contains no other groups which are reactive under the conditions of resin preparation herein described. The aliphatic glycols may accordingly be employed. Preferably the alkylene glycols and Aanhydride in the preparation or the product acl polyalkylene glycols are employed. Forexample,

alkylene glycols such as ethylene glycol, propylene glycol, (1,2-dihydroxybutane), (L3-dihydroxybutane) (1,4-dihydroxybutane) (2,3-dihydroxybutane), the amylene glycols, etc., may be employed. Examples of the polyalkylene glycols which may be used are diethylene glycol, triethylethyl alcohol have been found suitable in the process.

The rosin acid constituent of the ester cmployed may be gum rosin, wood rosin, substantially pure rosin acids obtained from said rosins, specific rosin acids as abietic acid, d-pimaric acid, l-pimaric acid, sapinic acid, etc., various natural or synthetic mixtures of said speciiic rosin acids. Furthermore, the rosin acid constituent may be a partially hydrogenated rosin acid. Any rosin acid wherein from 0 to about 70% of the total number of double bonds originally present (two:`

per rosin acid molecule) have been saturated with hydrogen can be employed. Practically, the del gree of saturation of a rosin acid may be evaluated by determining its thiocyanogen value. On this basis any rosin acid may be employed in accordance with this invention which has a thiocyanogen value between and 80. Synthetic resins prepared from such partially hydrogenated rosin acids are the substantial equivalents of resins prepared from unhydrogenated rosin acids. Completely hydrogenated rosin acids cannot, however, be employed; and resins derived from rosin acid esters wherein substantially more than 70% of the total number of double bonds of'the rosin acid component are saturated with hydrogen do not possess the unique properties described hereinbefore for the resins oi! the invention. Some ethylenic unsaturation must remain in the rosin acid ester employed.

The quantity of the dihydric alcohol used in accordance with this invention will be from about 0.70 mol to about 1.50 mols of the dihydric alcohol for each mol of total dicarboxylic acid. Quantities below 1 mol of the dihydric alcohol lead to ultimate products of relatively high acid number and are used only when high acid number resins, which are of value in the preparation of aqueous dispersions or'salts, are desired. For most purposes, between 1 mol and 1.30 mols of dlhydric alcohol are used for each mol ot totalk dicarboxylic acid. A slight .excess'oi' the alcohol is .desirable to obtain an ultimate product low in acid number.

The amount of phthalic acid (or the anhydride thereof) utilized is critical and should be from about 0.10 to about 0.67 mol per moi of total dicarboxylic acid, and the amount which may be used varies with the mol 'ratio of rosin ester to total dicarboxylic acid -as can be seen from Figure 1. It too little phthalic acid is employed, the resulting resin does not possess thev desirable characteristic oi' forming permanently clear solutions with vinyl acetate-chloride copolymers. On the other hand, if the amount of phthalic acid used is too high, the resulting resin does not possess the unique characteristic of .stability to heat at temperatures below 150 C. and the capacity to be cured to an infusible state by heating at above 200 C; In other words, such a resin is essentially thermoplastic in nature.

Similarly the amount of monohydric alcohol ester oi' a rosin acid must be critically controlled to obtain resins having the unique characteristic described for the resins of this invention. To achieve these characteristics, the monohydric alcohol ester may be employed in the amount of from 0.60 to 1.70 mols per mol of total discarboxylic acid as shownon Figure 1. y

Thereare two distinctmethods for obtaining the resins of this 'invention Both have been illustrated :in the examples. One method involves a stepwise reaction in contrast to the other in -which all ingredients 'are reacted simultaneously. The -following statements refer particu larly to the stepwise procedure of reaction which is regarded as preferable due to the ease of control which it permits.

In the rst stage, -thedihydric alcohol, the

alpha-beta-unsaturated' dicarboxylic acid and the mixture has dropped to a value below about and above about 30 by the phenol-redmethod. Preferably, the mixture is brought to an acid number between 50. and 100. The phenol-red method-of determining acid numbers is utilized for control since the determination is reproduceable whereas vother acid number methods such as titration with a phenolphthalein indicator give varying results from test to test because of a fading or shifting end points. The time required vfor this reaction stage varies from about 0.25 to about l0 hours, depending upon thetemperature used and the size of the reaction mass. Where higher temperatures in thev range are used and the mass is capableof being rapidly heated.. the time required for the reaction is relatively.

short.

When the first stage has been completed, the monohydric alcohol ester of a rosin acid is added to the mixture.l If desired, this ester may be preheated, for example, to 10G-250 C. in order to speed the reaction. The resulting mixture is then heated at a temperature between about 200 C. and about 300 C. preferably between about 230 C. and about 270 C. until the product has reached the desired state.

The second stage reaction is continued by maintaining the reaction temperature until the cure time of the resulting mass is less than fourmin 1;. utes, preferably, between about 40 seconds and e `themixtureiuullcasesleadstoauultimateeinabout 90 seconds, -as measured on the product after cooling. The reaction is readily controlled by making cure time tests as it proceeds and allowing for a drop 4in cure time during cooling o! the material. This drop is readily determined by experience with any given' size mass and any given type of container in which the resin is permitted to cool. Usually, the drop in curing time during c ooling o! the resin will not be in excess of 30 seconds. It will be appreciated that the reaction continues at an appreciable rate after heating has been'discontinued only as long as the temperature of the mass remains above about 200 C. The acid number of the resin is decreased during the second stage of reaction to a value of less 'than about 50 and preferably to a value between about 1 and about 15, the time required for this stage may vary between about 0.25 and about hours and in most cases will be between about 1 and about 6 hours. An alternative method for making the subject resins `is to simply heat the ingredients simultaneously at a temperature of from about 200 C. to about 300 C., preferably between about 230 C. and about 270 C. until the resulting mass has a cure time less than 4 minutos, preferably, between about 40 sec. and about 90 sec.. as measured on the product after cooling. When this method is employed, it is highly desirable to control the upheat. so that the temperature is gradually raised to the maximum desired over a period of. from 2 to 8 hours. Such procedure avoids any premature gelation tendencies. After the maximum temperature is reached, heating is continued for from 1 to 15 hours, normally from 4 to 8 hours to provide a product having the.

desirable characteristics herein described. -Itshould be understood that, whereas resins having the unique characteristics described result from the utilization of the processes described hereinabove, resins having these properties cannot be obtained by utilizing the stepwise procedure which involves ilrst reacting the rosin ester with the alpha-beta-unsaturated dicarboxylic acid and phthalic acid and then reacting the resulting product with a dihydric alcohol. When this procedure is employed, the resulting resins do not possess the unique characteristics of stability to heat at temperatures below 150 C. and the capacity to be cured to an insoluble infusible state at temperatures above 200 C'. Resins prepared by the last described procedure are essentially thermoplastic and very dark in color and for that reason areuseless in many commercial applications.

Irrespective of the method employed to prepare the subject resins, it is usually desirable to sparge theresins during the last hour oi' the reaction kwith nitrogen, hydrogen, carbon dioxide or other gas which is inert at the reaction temperature to remove any readily volatile material which may be present. If desired, the reaction vessel may be4 put under vacuum during the last 2 or 3 hours of the reaction in order to remove a small amount of unreacted monohydric alcohol rosin ester and to increase the hardness of the;

reaction mixture is cloudy for a time showing the existence'of two phases. However, agitation oi ele phase product.

The resinous products in accordance with this invention vary from balsams, i. e.. highly viscous t liquids, to hard resins. The melting point is aifected chieily by the particular dihvdric alcohol utilized and the proportion oi' monohydric aicohol rosin ester employed. 'Ihe resins prepared from ethylene glycol are generally nexible, moderately hard and substantially nontacky at room temperatures. lltesins prepared trom diethylcne glycol are generally ilexibie, sott and somewhat tacky at room temperatures. Similar resins prepared from triethylene glycol are generally soit and highly taclw at room temperatures.

The acid number of the product is below about 50 by the .phenol-red method and will be below about 25 unless it is desired to utilize the resin for thev preparation of salts or aqueous disper' sions. Normally, the acid number will be 1 to 15 by the phenol-red method. The cure time will in all cases be less than four minutes and where a resin is in the soluble, fusible state, it will be above zero.

Theresins in accordance vwith this invention are odorless. tasteless and highly resistant to greases and oils. They have high adhesion when applied from solvent solution or from the molten state to cellulosic materials, metals, glass, and synthetic resinous articles. stantially unreactive and usually are very low in content of double bonds as shown by thiocyanate' xl'ilues in most casos below 50 and usually about v '.I'he resins in the uncured state or soluble in benzene, toluene, coal tar naphthas, methyl acetate, ethyl acetate and similar ester solvents,

acetone, methyl ethyl ketone and similar lretones.l They are substantially insoluble in petroleum (aliphatic) hydrocarbons, in lower aliphatic alcohols; in paraiiin base mineral oil, in fats and in wax. They are compatible with nitrocellulose. cellulose acetate propionate, cellulose acetate butyrate and benzyl cellulose over a wide range of proportions and have a limited compatibilityA with ethyl cellulose. The resins are furthermore compatible with casein, chlorinated rubber, methylV and ethyl methacrylate polymers and melamine resins. Formulation with cellulose derivatives raises the softening point oi the resin and decreases tackiness. Although the resins are not soluble in many waxes, small amounts of wax may be added to compositions containing the resins with the eect of increasing the moisturevaporprooiness of iilms prepared from such compositions.

' One of the unique characteristics of the resins of this invention, which makes themv very useful commercially, is their compatibility with the vinyl resins generally. The resins are, for example, widely compatible with polyvinyl chloride; polyvinyl formal, polyvinyl butyral and vinyl acetate-chloride copolymers, and possess limited compatibility with polyvinyl acetate. The resins possess at the same time excellent solution compatibility with the vinyl resins, particularly the The resins are sub-` the vinyl resins 'per se. Hot-melt compositions containing the subject rins and the above-men- V tions, and as surface coatings.

A n outstanding characteristic of the resins in i 10 Thus. wood veneers or sheets may be coated with the resin from molten.. baths orby calendering and the sheets pressed together with the aid oi heat -to form a plywood.V Continued heating at accordance with this invention is theirsubstantially unlimited stability at elevated tempera-'- tures at which they are suiciently fluid to be' readily coated in the moltenstate, coupled with the property of curing at very high temperatures. These resins, in the molten state, possess a substantially lower viscosity than do the resins of the above-mentioned application S. N. 490,645,-

' which makes themmore readily adapted to hot melt coating applications. The resins in all cases are readily coated lfrom the molten state at below 150 C., for example, between about 110 C. and

about 145l C. Unlike the usual film-forming alkyd resins, theyl may be maintained in the fluid state for prolonged periods of time without curing and with substantially no increase inV viscosity. Forexample, they are characterized by a heat stability in excess of -16 hours at below 150 C., i. e., they do not cure upon being heated at below 150. C. for 16 hours. However, upon being h eated at 200 C. or to a higher temperature below that of decomposition, they cure to an infusible, insoluble state. e

Soluble resins in accordance vwith this inven- ,tion may be used for coating, in general, from 20D-300 C. renders vthe ,resinous binder unatfected by heat and solvents.

'I'he uncured resins of thisinvention are particularly useful in the 4formulation of compositions suitable for the manufacture of'phonograph records of both the iilled and unfilled-types. vIn the manuiactureof the unfilled types, any ofthe film-forming vinyl resins such as polyvinyl chloride, polyvinyl acetate, vinyl'acetate-chloride copolymers, polyvinyl formal, polyvinyl butyral, etc. are compounded with fromv 1 to 30% of theresins of this invention (total weight basis) and the resulting composition molded, usually under heat and pressure. Other iilm-formers which may be used in place oi' the vinyl resins are ethyl cellulose, cellulose acetate-propionate, cellulose acetate, butyrate, polyalkyl methacrylates and combinations of these 'various illmformers.y Small amounts of plasticizers such as dioctyl phthalate and/or other modifiers such as natural or synthetic waxes may be added as desired.

To make the filled types.v a binder is prepared on the basis of from 1 to'60% oi' the resins of this ings of the resin are particularly useful on fiexible webs such as paper, regenerated cellulose, cellulose derivative films, felts and woven textiles to which they may be applied by calendering or molten coating; Such Webs may also be impregnated with the resin from molten baths or solvent solutions with the effect of sizing and increasing the strength of the web. By using a large excess of impregnating and coating material, impervious sheeting such as varnished cloths may be prepared. For example, cambric passed throughv a viscous molten mixture comprising 84% of the resin in accordance with Example l, 10% of methyl hydroabietate, 3% of calcium stearate, and 3% of butyl stearate upon cooling sired.`

The present invention includes within its scope articles coated with the resin and particularly iiexible webs such asl paper and cloth coated therewith. The coatings may be left in the soluble, fusible ystatel or 4may be cured in situ to the ge1led infu sibl e state. The'coated articles include coated laminates-and laminated articlesheld together byl vadhesive coatings comprising the resins in accordance with this invention.

:- polymers. etc.

invention, from 5 to 99% of a hlm-former selected from those mentioned in the paragraph immediately preceding, shellac, nitrocellulose, synthetic Irubbers such as butadiene-styrene copolymers,

butadiene-acrylonitrile copolymers, or combinations of such llm-formers, and from 0 to190% of low cost or diluent resins such asVinsol (a petrol'eum hydrocarbon insoluble-resin obtained from' pine wood stumps), rosi'n, rosin' esters, ethylenic hydrocarbon polymers; polynucleararomatic hydrocarbon resins obtained as by-produc'ts in water gasl manufacture (Resinex) coumarone-indene vA moldable composition is then made on the basis of about- 15-40% binder and about (iO-85% filler such as'clay, Whiting, slate flour, carbon black, etc.

Not only can the resins of this invention be f employed as above indicated, but the resins of application S. N. 490,645 may be similarly em- .in making phonograph records.

The following are specic examples of formui lations suitable for compounding clear kand filled phonograph record compositions Clear Type CISG@ Carbon black.. 4Zinc stearato t These materials werev compounded ,i'n'accordance withthe usual procedure of the art. `In

-moldingfthe resulting ,coinpofitions under .heat u and pressure, it was found thatl they vexhibited exceptionally good flow characteristics,r in 'this respect much improved over similar compositions ll not containing the resin of Example l. At the same time, the finished records did not show any substantial diminution in flexural strength or wearing properties as compared with records prepared from similar compositions not containing the resin of Example i.

Parts Vinyl acetate-chloride copolymer.- 19.2 Resin of Example 1 8.0 Di-2-ethyl hexyl phthalate 4.8 Ground limestone 62.3 Short nbre asbestos 3.7 Titanium dioxide 2.0v

The ingredients may be varied such that the binder (exclusive of pigment or filler) contains from about 5% to about 95% of the subject resins and from about 5% to about 95% of the vinyl resin. The use of the resins of this invention in hoor tile compositions promotes the workability and moldability of the compositions without aifecting appreciably the strength of the finishe tile.

Where in the specification and claims reference is made to the phenol red method for determining acid number, it will be understood that the acid number is determined in accordance with the following procedure: Two to three grams of material are weighed to the nearest 0.001 gram into a 250 milliliter Erlenmeyer flask and dissolved therein in 85 milliliters of acetone, 1 5 milliliters of ethyl alcohol and six drops oi' phenol red indicator solution (1% phenol red in alcohol). The acetone-alcohol solution is titratedy to a pink endpoint with standardized alcoholic potassium hydroxide solution of a normality factor of approximately 0..6. The acid number is calculated as follows:

v Mlliliters KOH Solution X N. F. X 56.1 Amd No' Weight of Sample where N. F. is the normality factor of the potasslum hydroxide solution.

Where in the specification and claims the expression cure time is used, it will be understood to refer to the time required to render a small particle of the resin referred to infusible at 200 Initially, the nail has no effect on the streak as the wet resin flows together immediately behind the nail. However, after a time the wet resin sets and does not ilow together to maintain the shiny wet streak, i. e., the nail leaves `a mark in the previously wet streak. The time required for the wet streak to reach the point at which it sets in this manner, measured from the time the resin is applied to the hot plate, is the cure time. A cure time of in excess of ilve minutes is indicative of a material which cannot be cured by heat since any material requiring more than ilve minutes to become gummy under the conditions of the test cures, if at all. by oxidation rather than by simple heating. If the resin acts as a jelly on the hot plate initially, the cure time is considered zero.

All parts and percentages in the specification and claims are by weight unless otherwise specined.

What I claim and desire to protect by letters Patent is:

1. A resinous reaction product prepared from a dihydric alcohol, an alpha-beta-unsaturated dicarboxylic acid, phthalic acid and a monohydric alcohol ester of an acid selected from the group consisting of rosin' acids and partially hydrogenated rosin acids, the nonalcoholic reactants being employed in amounts defined by the area ABC of Figure 1. the dihydric alcohol being employed in the amount of from 0.70 to 1.50 mols per mol of total dicarboxylic acid. said resinous reaction product being characterized by fusibility, by solubility in benzene and ethyl acetate, by a phenol red acid number less than 50, by substantial stability to heat at temperatures below C., by the capacity to be cured to an infusible state by heat at above 200 C., by a cure time at 200 C. of less than 4 minutes and by the capacity to form permanently clear solutions with vinyl acetate-chloride copolymers, the ethylenic double bonds of the aforesaid partially hydrogenated rosin acids being not more than 70% hydrogenated, the said dilivdrie alcohol containing only hydroxyl groups as reactive substituents, and the said monohydric alcoholcontaining no reactive group other than hydroxyl. A

2. A resinous reaction product prepared from an aliphatic glycol, an alpha-beta-unsaturated dicarboxylic acid, phthalic acid. and a monohydric alcohol ester of an acid selected from the group consisting of rosin acids and partially hydrogenated rosin acids, the nonalcoholic reactants being employed in amounts defined by the area ABC of Figure 1, the aliphatic glycol being employed in the amount of from 0.70 to 1.50 mols per mol of total dicarboxylic acid, said resinous reaction product being characterized by fusibility, by solubility in benzene and ethyl acetate. by a phenol red acid number less than 50, by substantial stability to heat at temperatures below 150 C., by the capacity to be cured to an infusible state by heat at above 200 C.. by a cure time at 200 C. of less than 4 minutes and by the capacity` to form permanently clear solutions with vinyl acetate-chloride copolymers, the ethylenic double bonds of the aforesaid partially hydrogenated rosin acids being not more than 70 hydrogenated, the said dihydric alcohol containing only hydroxyl groups as reactive substituents, and the said monohydric alcohol containing no reactive group other than hydroxyl.

3. A resinous reaction product prepared from ethylene glycol, an alpha-beta-unsaturated dicarboxylic acid, phthalic acid and a monohydric alcohol ester of an acid from the group consisting of rosin acids and partially hydrogenated rosin acids, the nonalcoholic reactants being employed in amounts defined by theA area ABC of Figure l, the ethylene glycol being employedl in the amount of from 0.70 to 1.50 mols per mol of 'total dicarboxylic acid, said resinous reaction product being characterized by fusibility. by solubility in benzene and ethyl acetate, by a phenol red acid number less than 50, by substantial stability to heat at temperatures below 150 C., by the capacity to be cured to an infusible state by heat at above 200 C., by a cure time at 200 C. of less than 4 minutes andby the capacity to form permanently clear solutions with vinyl acetate-chloride copolymers, the ethylenic double bonds of the aforesaid partially hydrogenated rosin acids being not more than 70% hydrogenated, and said monohydric alcohol containing no reactive group other than hydroxyl.

4. A resinous reaction product prepared from diethylene glycol, an alpha-beta-unsaturated dicarboxylic acid, phthalic acid and a monohydric alcohol ester of an acid from the group consisting of rosin acids and partially hydrogenated rosin acids, the nonalcoholic reactants being employed in amounts deiined by the area ABC of Figure 1, the diethylene glycol being vemployed in the amount of from 0.70 to 1.50 mols per mol of total dicarboxylic acid, said resinous reaction product being characterized by fusibility, by solubility in benzene and ethyl acetate,by a phenol red acid number less than 50, by substantial stability to heat at temperatures below 150 C., by the capacity to be cured to an infusible state by heat at above 200 C., by a cure time at 200 C. of less than 4 minutes and by the capacity to form permanently clear solutions with vinyl acetatechloride copolymers, the ethylenic double bonds of the aforesaid partially hydrogenated rosin acids being not more than 70% hydrogenated,

monohydric alcohol ester oi an acid from the group consisting of rosin acids and partially hyy drogenated rosin acids, the nonalcoholic reactants being employed in amounts dened by the area ABC of Figure 1, the ethylene glycol being employed in the amount of from 0.70 to 1.50 mols per mol of total dicarboxylic acid, said resinous reaction product being characterized by fusibility, by solubility in benzene and ethyl acetate, by a phenol red acid number less than 50, by substantial stability to heat at temperatures below 150 C., by the capacity to be cured to an infusible state by heat at above 200 C., by a cure time at 200 C. of less than 4 minutes and by the capacity to form4 permanently clear solutions with vinyl acetate-chloride copolymers, the ethylenic double bonds of the aforesaid partially hydrogenated rosin acids being not more than 70% hydrogenated, and said monohydric alcohol containing no reactive group other than hydroxyl.

6. 'A resinous reaction product prepared from ethylene glycol, maleic acid, phthalic acid and the methyl ester of a rosin acid, the nonalcoholic reactants being employed in amounts dened by the area ABC of Figure '7, the ethylene glycol being employed in the amount of from 0.70 to 1.50 mols per mol of total dicarboxylic acids, said resinous reaction product being characterized by fusibility, by solubility in benzene and ethyl acetate, by a phenol red acid number less` than 50, by substantial stability to heat at temperatures below 150 C., by the capacityto be cured to an iniusible state by heat at above 200 C.,by a cure time at 200 C. of less than 4 minutes and by the 14 capacity to form permanently clear solutions with vinyl acetate-chloride copolymers.

7. A resinous reaction product prepared iror'n tate, by a phenol red acid number less than 50, by

substantial stability to heat at temperatures below 150 C., by the capacity to be cured to an ini fusible state by heat at above 200 C., by a cure time at 200 C. of less than 4 minutes and by the capacity to form permanently clear solutions with vinyl acetate-chloride copolymers.

8. A resinous reaction product prepared from diethylene glycol, maleic acid, phthalic acid and the methyl ester of a rosin acid, the nonalcoholic reactants being employed in amounts dened by the area ABC of Figure 1, the diethylene glycol being employed in the amount of from 0.70 to 1.50 mols per mol of total dicarboxylic acid, said resinous reaction product being characterized by fusibility, by solubility in benzene and ethyl acetate, by a phenol red acid number less than 50, by substantial stability to heat at temperatures below 150? C., by the capacity to be cured to an infusible state by heat at above 200 C., by a cure time at 200 C. of less than 4 minutes and by the capacity to form permanently clear solutions with vinyl acetate-chloride copolymers.

9. A'resinous reaction product prepared from an aliphatic glycol, an alpha-beta-unsaturated dicarboxylic acid, phthalic acid, and the methyl ester of an acid selected from the group consisting of rosin acids and partially hydrogenated rosin acids,A the nonalcoholic reactants being employed in amounts defined by the area ABC of Figure 1, the aliphatic glycol being employed in the amount of from 0.70 to 1.50 mols per mol of total dicarboxylic acid, said resinous reaction product being characterized by fusibility, by solubility in benzene and ethyl acetate, by a phenol,

red acid number less than 50, by substantial stability to heat at temperatures below 150 C.,.by the capacity to be cured to an infusible state by heat at above 200 C., by a cure time at 200 C. of less than 4 minutes and by the capacity to form permanently clear solutions with vinyl acetatechloride copolymers, the ethylenic double bonds of the ai'oresaidl partially hydrogenated rosin acids being not more than 70% hydrogenated, and the said aliphatic glycol containing only hydroxyl groups as reactive substituents.

CLARENCE D. ENDER.

REFERENCES CITED The following referenlccs are of record in the le' of this patent:

y UNITED STATES PATENTS Number 2,411,904 Spiller Dec. 3,1946 

